CN108794733B - Block copolymer compatilizer and application thereof - Google Patents
Block copolymer compatilizer and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention discloses a block copolymer compatilizer and application thereof. The block copolymer compatilizer is selected from one or more of polylactic acid-polyethylene glycol-polylactic acid triblock copolymer, polyethylene glycol-polylactic acid-polyethylene glycol triblock copolymer and monomethyl ether polyethylene glycol-polylactic acid diblock copolymer. The invention also provides application of the block copolymer compatilizer in full-biodegradable polyester alloy. The block copolymer compatilizer is used for improving the compatibility of the full-biodegradable polyester alloy, is added in a physical blending mode, and is positioned at the interface of a blend through the selectivity of the interaction between different chain segments in the molecules of the compatilizer and alloy components, so that the compatibilization effect is realized; can effectively avoid side reaction generated by compatibilization in the extrusion processing process, and the viscosity of the system does not change obviously and is easy to process.
Description
Technical Field
The invention relates to the technical field of high polymer materials. More particularly, it relates to a block copolymer compatibilizer and its use.
Background
With the development of national economy, high polymer materials have penetrated into various fields, and the application thereof is very wide. However, most of the polymer materials are difficult to biodegrade, and cause serious environmental pollution such as "white pollution" after use. With the high concern of people on environmental problems and the implementation of sustainable development strategies, the development of completely biodegradable polymer materials becomes one of the hot spots of research.
Polylactic acid (PLA) has wide application in the fields of industry, agriculture, biomedicine, food packaging and the like because of its advantages of high modulus, high tensile strength, good transparency, good thermal stability, complete biodegradation and the like. However, the application is limited by the defects of hard quality, poor toughness, poor impact capability and the like. Biodegradable polyester materials such as Polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene adipate-butylene glycol (PBA), polybutylene succinate-adipate-butylene glycol (PBSA), polybutylene terephthalate-adipate-butylene glycol (PBAT), polybutylene terephthalate-succinate-butylene glycol (PBST) and the like become ideal alloy materials for PLA due to high ductility. However, the thermodynamic incompatibility of the components leads to obvious phase separation of the blended materials, thereby causing the defects of poor tear resistance, difficult bonding of a seal, poor mechanical property and the like. Therefore, it is necessary to add a compatibilizer to improve the compatibility of the alloy material, so as to obtain a PLA alloy with good mechanical properties.
Patent 201610263725.9 teaches that using a transesterification catalyst as a compatibilizer results in a block copolymer compatibilized PLA/PBAT system during blending, reduces the surface tension between two phases of the composite, reduces the size of the dispersed phase, and effectively improves the PLA/PBAT compatibility. Patent 201110351017.8 uses isocyanate-based reactive compatibilizers to compatibilize the PLA/PBAT system, reduce surface tension, reduce dispersed phase size, and improve two-phase compatibility. But the reactive and ester exchange catalyst compatilizer has more side reactions in the melt extrusion process and lower compatibilization efficiency; and the viscosity of the blend is increased in the reaction, the processing difficulty is improved, and the high-efficiency interfacial compatilizer cannot be obtained.
Therefore, the invention provides a block copolymer compatilizer for PLA and biodegradable polyester alloy and application thereof.
Disclosure of Invention
An object of the present invention is to provide a block copolymer compatibilizer.
Another object of the present invention is to provide an application of the block copolymer compatibilizer.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a block copolymer compatibilizer selected from one or more of a polylactic acid-polyethylene glycol-polylactic acid (i.e., PLA-PEG-PLA) triblock copolymer, a polyethylene glycol-polylactic acid-polyethylene glycol (i.e., PEG-PLA-PEG) triblock copolymer, and a monomethyl ether polyethylene glycol-polylactic acid (i.e., MPEG-PLA) diblock copolymer.
Preferably, the number average molecular weight of the polylactic acid-polyethylene glycol-polylactic acid (i.e. PLA-PEG-PLA) triblock copolymer is 8000-40000 g/mol, wherein the number average molecular weight of the PEG chain segment is 2000-15000 g/mol. Further, in some embodiments of the present invention, the number average molecular weight of the PLA-PEG-PLA triblock copolymer is, for example, 8000-10000 g/mol, 8000-18000 g/mol, 8000-22000 g/mol, 8000-30000 g/mol, 10000-18000 g/mol, 10000-22000 g/mol, 10000-30000 g/mol, 10000-40000 g/mol, 18000-22000 g/mol, 18000-30000 g/mol, 18000-40000 g/mol, 22000-30000 g/mol, 22000-40000 g/mol, etc.; wherein the number average molecular weight of the PEG chain segment is 2000-4000 g/mol, 2000-5000 g/mol, 2000-8000 g/mol, 2000-10000 g/mol, 2000-13000 g/mol, 4000-5000 g/mol, 4000-8000 g/mol, 4000-10000 g/mol, 4000-13000 g/mol, 4000-15000 g/mol, 5000-8000 g/mol, 5000-10000 g/mol, 5000-13000 g/mol, 5000-15000 g/mol, 8000-10000 g/mol, 8000-13000 g/mol, 8000-15000 g/mol, 10000-13000 g/mol, 10000-15000 g/mol, 13000-15000 g/mol, etc. A large number of experimental researches prove that the fully biodegradable polyester alloy prepared by the PLA-PEG-PLA triblock copolymer compatilizer with the number average molecular weight range has better compatibilization effect.
Preferably, the number average molecular weight of the polyethylene glycol-polylactic acid-polyethylene glycol (PEG-PLA-PEG) triblock copolymer is 4000-40000 g/mol, wherein the number average molecular weight of the PEG chain segment is 1000-20000 g/mol. Further, in some embodiments of the present invention, the PEG-PLA-PEG triblock copolymer has a number average molecular weight of, for example, 4000 to 8000g/mol, 4000 to 10000g/mol, 4000 to 18000g/mol, 4000 to 30000g/mol, 8000 to 10000g/mol, 8000 to 18000g/mol, 8000 to 30000g/mol, 8000 to 40000g/mol, 10000 to 18000g/mol, 10000 to 30000g/mol, 10000 to 40000g/mol, 18000 to 30000g/mol, 18000 to 40000g/mol, 30000 to 40000g/mol, and the like; wherein the number average molecular weight of the PEG chain segment is 1000-2000 g/mol, 1000-6000 g/mol, 1000-15000 g/mol, 2000-6000 g/mol, 2000-15000 g/mol, 2000-20000 g/mol, 6000-15000 g/mol, 6000-20000 g/mol, 15000-20000 g/mol, etc. A large number of experimental researches prove that the fully biodegradable polyester alloy prepared by the PEG-PLA-PEG triblock copolymer compatilizer with the number average molecular weight range has better compatibilization effect.
Preferably, the number average molecular weight of the two-block copolymer of monomethyl ether polyethylene glycol-polylactic acid (MPEG-PLA) is 2000-30000 g/mol, wherein the number average molecular weight of the PEG chain segment is 1000-15000 g/mol. Further, in some embodiments of the present invention, the MPEG-PLA diblock copolymer has a number average molecular weight of, for example, 2000 to 19000g/mol, 2000 to 20000g/mol, 19000 to 30000g/mol, 20000 to 30000g/mol, and the like; wherein the number average molecular weight of the PEG chain segment is 1000-2000 g/mol, 1000-4000 g/mol, 2000-15000 g/mol, 4000-15000 g/mol, etc. A large number of experimental researches prove that the fully biodegradable polyester alloy prepared by the MPEG-PLA diblock copolymer compatilizer with the number average molecular weight range has better compatibilization effect.
In order to achieve the second purpose, the invention adopts the following technical scheme:
an application of the block copolymer compatilizer in full-biodegradable polyester alloy. The block copolymer compatilizer is used for improving the compatibility of the full-biodegradable polyester alloy, is added in a physical blending mode, and is positioned at the interface of a blend through the selectivity of the interaction between different chain segments in the molecules of the compatilizer and alloy components, so that the compatibilization effect is realized; can effectively avoid side reaction generated by compatibilization in the extrusion processing process, and the viscosity of the system does not change obviously and is easy to process.
Preferably, the fully biodegradable polyester alloy is an alloy of polylactic acid (PLA) and biodegradable polyester. According to the invention, the block copolymer compatilizer is applied to PLA and a biodegradable polyester material for compatibilization, so that the compatibility of the polyester alloy is effectively improved, and the fully biodegradable polyester alloy with excellent performance is obtained.
Preferably, the biodegradable polyester is selected from one or more of Polycaprolactone (PCL), polybutylene succinate-butylene glycol (PBS), polybutylene adipate-butylene glycol (PBA), polybutylene succinate-adipate-butylene glycol (PBSA), polybutylene terephthalate-adipate-butylene glycol (PBAT) and polybutylene terephthalate-succinate-butylene glycol (PBST).
Preferably, the application specifically comprises the following steps: and blending the block copolymer compatilizer, polylactic acid and biodegradable polyester to prepare the fully biodegradable polyester alloy.
Preferably, the blending temperature is 130-220 ℃, and the blending time is 5-60 min. Further, in certain embodiments of the present invention, the temperature of the blending is, for example, 130 to 180 ℃, 180 to 220 ℃, etc.; the blending time is, for example, 5 to 20min, 5 to 30min, 5 to 60min, 20 to 30min, 20 to 60min, 30 to 60min, etc.
Preferably, the blending is carried out in an internal mixer.
Preferably, the use amount of the block copolymer compatilizer is 0.1-10 wt% of the total mass of the polylactic acid and the biodegradable polyester. Further, in some embodiments of the present invention, the block copolymer compatibilizer is used in an amount of 0.1 to 3 wt%, 3 to 10wt%, or the like, based on the total mass of the polylactic acid and the biodegradable polyester. A large number of experimental researches prove that the prepared fully biodegradable polyester alloy has better compatibilization effect within the dosage range of the block copolymer compatilizer.
In addition, unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.
The invention has the following beneficial effects:
the block copolymer compatilizer provided by the invention can be used for improving the compatibility of the full-biodegradable polyester alloy, and the block copolymer compatilizer moves to a two-phase interface of PLA and biodegradable polyester under the action of shearing force in the melt blending process, so that the interfacial tension is reduced, the interfacial adhesion is improved, and the interfacial stability is improved. The principle is that the free energy of a blending system is reduced by the block copolymer in the blending process, the system is in the state of minimum free energy, and the block copolymer is self-assembled at an interface, so that the interface compatibility is improved. The polylactic acid chain segment in the block copolymer is mixed with PLA, and the polyethylene glycol chain segment is intertwined with the chain segment of the biodegradable polyester to form a stable interface structure, so that the compatibility of the biodegradable polyester alloy is improved, the size of a disperse phase is reduced, and the fully biodegradable polyester alloy with excellent performance is obtained.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows a graph of the change in mechanical properties of the alloys of comparative example 1 and example 1 according to the invention.
FIG. 2 shows a scanning electron micrograph of an alloy prepared according to example 1 of the present invention.
FIG. 3 shows a scanning electron micrograph of an alloy prepared according to comparative example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The main reagents used in the embodiments of the invention:
lactide (LA): j & K, analytically pure;
polyethylene glycol (PEG): j & K, analytically pure;
monomethyl ether polyethylene glycol (MPEG): j & K, analytically pure;
stannous octoate (Sn (Oct)2)：J&Company K, analytical grade;
dicyclohexylmethane diisocyanate (HMDI): j & K company, analytically pure.
The synthesis method of the polylactic acid-polyethylene glycol-polylactic acid and monomethyl ether polyethylene glycol-polylactic acid block copolymer in the specific embodiment of the invention comprises the following steps:
adding PEG and LA or MPEG and LA into a three-neck flask with a stirrer, reacting for 24h under the protection of nitrogen at 135 ℃ by using stannous octoate as a catalyst, and cooling and drying for later use.
The synthesis method of the polyethylene glycol-polylactic acid-polyethylene glycol block copolymer in the specific embodiment of the invention comprises the following steps:
adding a monomethyl ether polyethylene glycol-polylactic acid block copolymer and HMDI into a three-neck flask with a stirrer, reacting for 6h under the protection of nitrogen at 60 ℃ by taking toluene as a solvent, separating out, purifying, cooling and drying for later use.
According to the synthesis method, a series of polylactic acid-polyethylene glycol-polylactic acid and monomethyl ether polyethylene glycol-polylactic acid block copolymers are synthesized by controlling the molar ratio of MPEG to LA and the molar ratio of PEG to LA.
According to the synthesis method, a series of polyethylene glycol-polylactic acid-polyethylene glycol block copolymers are synthesized by controlling the reaction of monomethyl ether-polylactic acid block copolymers with different chain segment ratios and HMDI.
In the present invention, the preparation methods are all conventional methods unless otherwise specified. The starting materials used are commercially available from published sources unless otherwise specified.
Example 1
A full-biodegradable polyester alloy adopts PLA-PEG-PLA triblock copolymer compatilizer, the number average molecular weight of the compatilizer is 22000g/mol, and the molecular weight of a PEG chain segment is 4000 g/mol; the preparation method comprises the following steps:
70g of PLA, 30g of PBAT and 3g of PLA-PEG-PLA are dried and then added into an internal mixer for blending for 10min at 180 ℃ to prepare the fully biodegradable polyester alloy, namely PLA/PBAT/PLA-PEG-PLA alloy, and the mixture is dried for later use.
Example 2
A full-biodegradable polyester alloy adopts PLA-PEG-PLA triblock copolymer compatilizer, the number average molecular weight of the compatilizer is 40000g/mol, and the molecular weight of a PEG chain segment is 6000 g/mol; the preparation method comprises the following steps:
70g of PLA, 30g of PBAT and 3g of PLA-PEG-PLA are dried and then added into an internal mixer for blending for 10min at 180 ℃ to prepare the fully biodegradable polyester alloy, namely PLA/PBAT/PLA-PEG-PLA alloy, and the mixture is dried for later use.
Example 3
A full-biodegradable polyester alloy adopts PLA-PEG-PLA triblock copolymer compatilizer, the number average molecular weight of the compatilizer is 22000g/mol, and the molecular weight of a PEG chain segment is 4000 g/mol; the preparation method comprises the following steps:
70g of PLA, 30g of PBAT and 10g of PLA-PEG-PLA are dried and then added into an internal mixer for blending for 10min at 220 ℃ to prepare the fully biodegradable polyester alloy, namely PLA/PBAT/PLA-PEG-PLA alloy, and the mixture is dried for later use.
Example 4
A full-biodegradable polyester alloy adopts PLA-PEG-PLA triblock copolymer compatilizer, the number average molecular weight of the compatilizer is 22000g/mol, and the molecular weight of a PEG chain segment is 4000 g/mol; the preparation method comprises the following steps:
70g of PLA, 30g of PBAT and 3g of PLA-PEG-PLA are dried and then added into an internal mixer for blending for 10min at 220 ℃ to prepare the fully biodegradable polyester alloy, namely PLA/PBAT/PLA-PEG-PLA alloy, and the mixture is dried for later use.
Example 5
A full-biodegradable polyester alloy adopts PLA-PEG-PLA triblock copolymer compatilizer, the number average molecular weight of the compatilizer is 22000g/mol, and the molecular weight of a PEG chain segment is 4000 g/mol; the preparation method comprises the following steps:
70g of PLA, 30g of PBAT and 3g of PLA-PEG-PLA are dried and then added into an internal mixer for blending for 40min at 180 ℃ to prepare the fully biodegradable polyester alloy, namely PLA/PBAT/PLA-PEG-PLA alloy, and the mixture is dried for later use.
Example 6
A full-biodegradable polyester alloy adopts PEG-PLA-PEG triblock copolymer compatilizer, the number average molecular weight of the compatilizer is 8000g/mol, wherein the molecular weight of a PEG chain segment is 2000 g/mol; the preparation method comprises the following steps:
60g of PLA, 40g of PBSA and 3g of PEG-PLA-PEG are dried and then added into an internal mixer for blending for 10min at 180 ℃ to prepare the fully biodegradable polyester alloy, namely PLA/PBSA/PEG-PLA-PEG alloy, and the mixture is dried for later use.
Example 7
A full biodegradable polyester alloy, the alloy adopts MPEG-PLA two block copolymer compatilizer, the number average molecular weight of the compatilizer is 19000g/mol, wherein the molecular weight of PEG chain segment is 2000 g/mol; the preparation method comprises the following steps:
80g of PLA, 20g of PBS and 10g of MPEG-PLA are dried and then added into an internal mixer for blending for 10min at 180 ℃ to prepare the fully biodegradable polyester alloy, namely PLA/PBS/MPEG-PLA alloy, and the fully biodegradable polyester alloy is dried for later use.
Comparative example 1
After 70g of PLA and 30g of PBAT are dried, the PLA/PBAT alloy is added into an internal mixer to be blended for 10min at 180 ℃ to prepare the PLA/PBAT alloy, and the PLA/PBAT alloy is dried for standby.
Comparative example 2
After 60g of PLA and 40g of PBSA are dried, the PLA and the PBSA are added into an internal mixer to be blended for 10min at 180 ℃, and the fully biodegradable polyester alloy, namely the PLA/PBSA alloy, is prepared and dried for later use.
Comparative example 3
80g of PLA and 20g of PBS are dried and then added into an internal mixer to be blended for 10min at 180 ℃, and the fully biodegradable polyester alloy, namely the PLA/PBS alloy, is prepared and dried for later use.
Test example:
the materials prepared in the above examples and comparative examples were subjected to the following tests:
the dried alloy material was injection molded into tensile bars using a micro injection molding machine (Thermo Scientific Mini JETPRO), bar gauge: 25mm × 4mm × 2mm, the samples were subjected to mechanical testing (Instron-5699) according to ASTM D638 under 50 mm/min.
The internal microstructure of the alloy was observed by Scanning Electron Microscope (SEM) (Hitachi S-4800), and the sample was brittle-broken in liquid nitrogen before observation and subjected to gold-spraying treatment.
Table 1 shows the results of various performance tests of the alloys prepared in examples 1-7 and comparative examples 1-3.
Table 1 results of performance testing
| Tensile Strength (MPa) | Elongation at Break (%) | Particle size of dispersed phase (μm) | |
| Comparative example 1 | 54.3±2.0 | 23.2±4.2 | ～2.5 |
| Example 1 | 53.1±3.0 | 173.4±15.3 | ～0.5 |
| Example 2 | 54.1±3.4 | 153.5±3.4 | ～0.6 |
| Example 3 | 53.8±4.3 | 115.3±12.5 | ～0.7 |
| Example 4 | 51.1±3.0 | 123.4±15.3 | ～0.5 |
| Example 5 | 53.2±3.2 | 150.4±3.4 | ～0.5 |
| Comparative example 2 | 55.4±2.3 | 15.4±1.4 | ～2.7 |
| Example 6 | 54.2±3.3 | ·199.3±12.5 | ～0.6 |
| Comparative example 3 | 59.4±2.1 | 11.4±2.3 | ～2.3 |
| Example 7 | 58.7±2.4 | 101.4±2.3 | ～0.4 |
The tensile strength and elongation at break of the alloys in comparative example 1 and example 1 are shown in figure 1, the data are shown in table 1, and after the PLA-PEG-PLA triblock copolymer compatilizer is added, the elongation at break is obviously improved to 173%; while the elongation at break of the alloy without the addition of the compatibilizer was only 23%. The tensile strength of the alloy in example 1 was slightly lowered, but was maintained at 53MPa or more.
SEM photographs of the alloys of example 1 and comparative example 1 As shown in FIGS. 2 and 3, after addition of the PLA-PEG-PLA triblock copolymer compatibilizer, the interfacial phase blurred, the size of the dispersed phase of PBAT decreased significantly, the particle size was less than 0.5 μm (Table 1), and the PBAT dispersed more uniformly, tending to form a continuous phase structure. Therefore, the addition of the block copolymer effectively improves the interfacial compatibility of PLA and PBAT, improves the toughness of the alloy and greatly improves the elongation at break of the alloy.
The performance test results of examples 2-5 and comparative example 1, example 6 and comparative example 2, and example 7 and comparative example 3 show that the addition of the block copolymer compatilizer effectively reduces the size of the dispersed phase, greatly improves the elongation at break of the alloy, and effectively improves the compatibility of the alloy.
Examples 8 to 13
The preparation method and the adopted compatilizer of the fully biodegradable polyester alloy are the same as those of the example 1, and the alloy performance test method is the same as that of the test example, except that the number average molecular weight of the compatilizer is different from the number average molecular weight of a PEG chain segment in the compatilizer, and the result is shown in Table 2.
Examples 14 to 16
The preparation method and the adopted compatilizer of the fully biodegradable polyester alloy are the same as those of the embodiment 1, and the alloy performance testing method is the same as that of the testing example, except that the addition proportion of the compatilizer is different, and the result is shown in the table 2.
Examples 17 to 18
The preparation method and the adopted compatilizer of the fully biodegradable polyester alloy are the same as those of the embodiment 1, and the alloy performance testing method is the same as that of the testing example, except that the blending temperature is different, and the results are shown in the table 2.
Examples 19 to 20
The preparation method and the adopted compatilizer of the fully biodegradable polyester alloy are the same as those of the embodiment 1, and the alloy performance testing method is the same as that of the testing example, except that the blending time is different, and the results are shown in the table 2.
Examples 21 to 26
The preparation method and the used compatilizer of the fully biodegradable polyester alloy are the same as those of the example 6, and the alloy performance test method is the same as that of the test example, except that the number average molecular weight of the compatilizer is different from that of a PEG chain segment in the compatilizer, and the result is shown in Table 3.
Examples 27 to 29
The preparation method and the used compatilizer of the fully biodegradable polyester alloy are the same as those of the example 6, and the alloy performance test method is the same as that of the test example, except that the addition ratio of the compatilizer is different, and the result is shown in the table 3.
Examples 30 to 31
The preparation method and the adopted compatilizer of the fully biodegradable polyester alloy are the same as those of the example 6, and the alloy performance testing method is the same as that of the testing example, except that the blending temperature is different, and the results are shown in the table 3.
Examples 32 to 33
The preparation method and the adopted compatilizer of the fully biodegradable polyester alloy are the same as those of the example 6, and the alloy performance testing method is the same as that of the testing example, except that the blending time is different, and the results are shown in the table 3.
Examples 34 to 39
The preparation method and the used compatilizer of the fully biodegradable polyester alloy are the same as those of the example 7, and the alloy performance test method is the same as that of the test example, except that the number average molecular weight of the compatilizer is different from that of the PEG chain segment in the compatilizer, and the result is shown in Table 4.
Examples 40 to 41
The preparation method and the used compatilizer of the fully biodegradable polyester alloy are the same as those of the example 7, and the alloy performance test method is the same as that of the test example, except that the addition ratio of the compatilizer is different, and the results are shown in Table 4.
Examples 42 to 43
The preparation method and the adopted compatilizer of the fully biodegradable polyester alloy are the same as those of the example 7, and the alloy performance testing method is the same as that of the testing example, except that the blending temperature is different, and the results are shown in the table 4.
Examples 44 to 45
The preparation method and the used compatilizer of the fully biodegradable polyester alloy are the same as those of the example 7, and the alloy performance testing method is the same as that of the testing example, except that the blending time is different, and the results are shown in the table 4.
Table 2 results of performance testing
Note: "-" indicates that this item is unchanged from example 1.
Table 3 results of performance testing
Note: "-" indicates that this item does not change from example 6.
Table 4 results of performance testing
Note: "-" indicates that this item is unchanged from example 7.
The results show that: the number average molecular weight of the compatilizer and the number average molecular weight of a PEG chain segment in the compatilizer have obvious influence on the compatibilization effect of the fully biodegradable polyester alloy, and the excessively high molecular weight has overlarge viscosity and is not beneficial to moving to a two-phase interface; when the molecular weight is too low, the interfacial tension cannot be effectively reduced, the chain segment entanglement ratio is poor, and the alloy is unstable; the addition proportion of the block copolymer compatilizer can keep higher tensile strength and higher elongation at break in a certain range, the proportion of the block copolymer compatilizer is continuously increased, the tensile strength is obviously reduced, the elongation at break is not further enhanced, the phase size is not obviously changed, and the block copolymer becomes a single phase in the alloy; when the blending time and the blending temperature of the alloy meet certain requirements, the alloy with excellent performance can be obtained, the mixing is not uniform when the temperature is too low, and the compatilizer cannot be transported to an interface to play a compatilizer role; the alloy is degraded at a high temperature, the tensile strength and the elongation at break are obviously reduced, the longer the blending time is, the more obvious the degradation is, and the more obvious the performance is reduced. Therefore, the number average molecular weight of the compatilizer and the molecular weight of the PEG chain segment are effectively controlled, the adding proportion of the block copolymer is adjusted, the reasonable blending time and blending temperature are designed, the full-biological polyester alloy with excellent performance can be obtained, and the compatilizer of the block copolymer can effectively improve the compatibility of the biodegradable polyester.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (1)
1. The application of the block copolymer compatilizer in the full-biodegradable polyester alloy is characterized in that the block copolymer compatilizer is selected from one or more of polylactic acid-polyethylene glycol-polylactic acid triblock copolymer and monomethyl ether polyethylene glycol-polylactic acid diblock copolymer;
the application specifically comprises the following steps: blending the block copolymer compatilizer, polylactic acid and biodegradable polyester to prepare fully biodegradable polyester alloy;
the biodegradable polyester is selected from one or more of polycaprolactone, poly (butylene succinate) -butylene adipate, poly (butylene succinate) -adipate, poly (terephthalic acid-adipate-butylene glycol) and poly (terephthalic acid-butylene succinate);
the number average molecular weight of the polylactic acid-polyethylene glycol-polylactic acid triblock copolymer is 8000-40000 g/mol, wherein the number average molecular weight of the PEG chain segment is 2000-15000 g/mol;
the number average molecular weight of the monomethyl ether polyethylene glycol-polylactic acid diblock copolymer is 2000-30000 g/mol, wherein the number average molecular weight of the PEG chain segment is 1000-15000 g/mol;
the blending temperature is 130-220 ℃, and the blending time is 5-60 min;
the dosage of the block copolymer compatilizer is 0.1-10 wt% of the total mass of the polylactic acid and the biodegradable polyester.
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| CN102219892A (en) * | 2010-06-30 | 2011-10-19 | 上海谊众生物技术有限公司 | Preparation method of polyethylene glycol monomethyl ether-dl-polylactic acid block copolymer |
| CN104164067A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Microporous plastic film |
| CN106995528A (en) * | 2016-01-26 | 2017-08-01 | 浙江大学 | A kind of process for purification of mPEG-PDLLA |
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| CN102219892A (en) * | 2010-06-30 | 2011-10-19 | 上海谊众生物技术有限公司 | Preparation method of polyethylene glycol monomethyl ether-dl-polylactic acid block copolymer |
| CN104164067A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Microporous plastic film |
| CN106995528A (en) * | 2016-01-26 | 2017-08-01 | 浙江大学 | A kind of process for purification of mPEG-PDLLA |
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| Compatibilization effect of poly(epsilon-caprolactone)-b-poly(ethylene glycol) block copolymers and phase morphology analysis in immiscible poly(lactide)/poly(epsilon-caprolactone) blends;Na YH;《BIOMACROMOLECULES》;20021130;第3卷(第6期);第1179-1186页 * |
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